JP7158087B1 - Method for producing semiconducting single-walled carbon nanotube dispersion - Google Patents

Abstract

[PROBLEMS] To provide a method for producing a semiconducting SWCNT dispersion, which enables both high separation between semiconducting SWCNT and metallic SWCNT and dispersion stability of the semiconducting SWCNT dispersion. SOLUTION: In one aspect of the present disclosure, after centrifuging a SWCNT dispersion to be separated containing SWCNTs including semiconducting SWCNTs and metallic SWCNTs, an aqueous medium, and a polymer, the semiconducting SWCNTs are separated. wherein the polymer is a structural unit A derived from a monomer represented by the following formula (1) and a monomer represented by the following formula (3) The present invention relates to a method for producing a semiconducting single-walled carbon nanotube dispersion, which is a copolymer containing a structural unit B derived from. CH2=CR0-COOM (1) CH2=CR5-COO-(EO)p-(PO)q-R6 (3) [Selection diagram] None

Description

The present disclosure provides a method for producing a semiconducting single-walled carbon nanotube dispersion, a method for producing a semiconducting single-walled carbon nanotube including the production method as a process, and a method for separating a metallic single-walled carbon nanotube and a semiconducting single-walled carbon nanotube. etc.

In recent years, nanometer-sized carbon materials are expected to be applied to various fields due to their physical and chemical properties. One such material is a carbon nanotube (hereinafter sometimes referred to as "CNT"). A CNT has a structure in which a graphene sheet is rolled into a cylindrical shape, and a CNT consisting of only one layer of a cylinder is called a single-walled carbon nanotube (hereinafter also referred to as “SWCNT”). is

CNTs are known to have different electrical properties and the like depending on the winding method, diameter, and the like of the graphene sheet. In particular, since SWCNTs are greatly affected by the quantum effect, there are those that exhibit metallic properties (metallic SWCNTs) and those that exhibit semiconducting properties (semiconductor type SWCNTs). As a method for producing SWCNT, synthesis methods such as a high-pressure carbon monoxide disproportionation method (HiPco method), an improved direct injection pyrolysis synthesis method (e-DIPS method), an arc discharge method, and a laser ablation method are known. However, at present, no technology for producing only one type of CNT has been established, and when SWCNT is applied to various uses, it is possible to separate the desired type of SWCNT from the mixture. Needed. Metallic SWCNTs are expected to be used for touch panels, transparent electrodes for solar cells, fine wiring of devices, etc. by utilizing their excellent conductivity, and semiconducting SWCNTs are applied to transistors, sensors, etc. is expected.

Several methods for separating metallic SWCNTs and semiconducting SWCNTs have already been reported. Patent Document 1 discloses separation of metallic SWCNTs in a dispersion liquid of SWCNTs to be separated by using a specific copolymer as a separating agent. A separation method is disclosed in which SWCNT and semiconducting SWCNT can be separated by a simple operation. Specifically, after centrifuging a SWCNT dispersion to be separated containing polyacrylic acid as a dispersant, a semiconducting SWCNT dispersion including a step of collecting a supernatant containing semiconducting SWCNTs from the centrifuged dispersion. A method of making the liquid is disclosed.

JP 2019-202912 A

In addition to high separability of semiconducting SWCNTs, it is also desired that the resulting semiconducting SWCNT dispersion liquid has good dispersion stability.

In one aspect, the present disclosure is a method for producing a semiconducting SWCNT dispersion, and a method for producing a semiconducting SWCNT, which enables both high separability of semiconducting SWCNT and dispersion stability of the obtained semiconducting SWCNT dispersion. and a method for separating metallic SWCNTs. In one aspect, the present disclosure relates to a method for producing semiconducting SWCNTs and a method for producing an ink containing semiconducting SWCNTs, which includes the production method as one step, and in one aspect, to an ink containing semiconducting SWCNTs.

式（２）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴はそれぞれ独立に、水素原子、又は水酸基を有していてもよい炭素数が１以上２以下のアルキル基を示す。
ＣＨ₂＝ＣＲ⁵－ＣＯＯ－（ＥＯ）_p－（ＰＯ）_q－Ｒ⁶ （３）
式（３）中、Ｒ⁵は水素原子、またはメチル基を示す。Ｒ⁶は水素原子、または炭素数が１以上５以下の炭化水素基を示し、ＥＯはエチレンオキシ基、ＰＯはプロピレンオキシ基を示し、pはエチレンオキシ基の平均付加モル数を示し、１以上１２０以下であり、ｑはプロピレンオキシ基の平均付加モル数を示し、０以上５０以下である。 In one aspect, the present disclosure provides:
preparing a SWCNT dispersion to be separated, comprising SWCNTs including semiconducting SWCNTs and metallic SWCNTs, an aqueous medium, and a polymer;
After centrifuging the to-be-separated SWCNT dispersion, collecting a supernatant liquid containing the semiconducting SWCNT from the centrifuged to-be-separated SWCNT dispersion,
The polymer is a copolymer containing a structural unit A derived from a monomer represented by the following formula (1) and a structural unit B derived from a monomer represented by the following formula (3) , relates to a method for producing a semiconducting SWCNT dispersion.
_CH2 ⁼ CR0-COOM (1)
In formula (1), R ⁰ represents a hydrogen atom or a methyl group. M represents any one of a hydrogen atom, a metal atom, and a group having a structure represented by the following formula (2).

In formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 or more and 2 or less carbon atoms which may have a hydroxyl group.
_CH2 =CR5- ^COO- (EO) _p- (PO) _q -R6 ( ³ )
In formula ( ³ ), R5 represents a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, p represents the average number of added moles of ethyleneoxy groups, and is 1 or more. It is 120 or less, and q represents the average added mole number of propyleneoxy groups, and is 0 or more and 50 or less.

In one aspect, the present disclosure is a method for producing semiconducting SWCNTs, comprising a step of collecting semiconducting SWCNTs by filtering a semiconducting SWCNT dispersion obtained by the method for producing a semiconducting SWCNT dispersion of the present disclosure. Regarding.

In one aspect of the present disclosure, a step of drying the semiconducting SWCNT dispersion obtained by the method for producing a semiconducting SWCNT dispersion of the present disclosure to obtain a mixture containing the semiconducting SWCNTs and the copolymer; The present invention relates to a method for producing semiconducting SWCNTs, including a step of removing the copolymer from the mixture and collecting semiconducting SWCNTs.

式（２）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴はそれぞれ独立に、水素原子、又は水酸基を有していてもよい炭素数が１以上２以下のアルキル基を示す。
ＣＨ₂＝ＣＲ⁵－ＣＯＯ－（ＥＯ）_p－（ＰＯ）_q－Ｒ⁶ （３）
式（３）中、Ｒ⁵は水素原子、またはメチル基を示す。Ｒ⁶は水素原子、または炭素数が１以上５以下の炭化水素基を示し、ＥＯはエチレンオキシ基、ＰＯはプロピレンオキシ基を示し、pはエチレンオキシ基の平均付加モル数を示し、１以上１２０以下であり、ｑはプロピレンオキシ基の平均付加モル数を示し、０以上５０以下である。 In one aspect, the present disclosure provides:
preparing a SWCNT dispersion to be separated, comprising SWCNTs including semiconducting SWCNTs and metallic SWCNTs, an aqueous medium, and a polymer;
After centrifuging the to-be-separated SWCNT dispersion, collecting a supernatant liquid containing the semiconducting SWCNT from the centrifuged to-be-separated SWCNT dispersion,
The polymer is a copolymer containing a structural unit A derived from a monomer represented by the following formula (1) and a structural unit B derived from a monomer represented by the following formula (3) , a method for separating semiconducting SWCNTs and metallic SWCNTs.
_CH2 ⁼ CR0-COOM (1)
In formula (1), R ⁰ represents a hydrogen atom or a methyl group. M represents any one of a hydrogen atom, a metal atom, and a group having a structure represented by the following formula (2).

In formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 or more and 2 or less carbon atoms which may have a hydroxyl group.
_CH2 =CR5- ^COO- (EO) _p- (PO) _q -R6 ( ³ )
In formula ( ³ ), R5 represents a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, p represents the average number of added moles of ethyleneoxy groups, and is 1 or more. It is 120 or less, and q represents the average added mole number of propyleneoxy groups, and is 0 or more and 50 or less.

In one aspect, the present disclosure relates to a method for producing a semiconducting SWCNT-containing ink that includes the method for producing a semiconducting SWCNT dispersion of the present disclosure or the method for producing semiconducting SWCNTs of the present disclosure as one step.

式（２）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴はそれぞれ独立に、水素原子、又は水酸基を有していてもよい炭素数が１以上２以下のアルキル基を示す。
ＣＨ₂＝ＣＲ⁵－ＣＯＯ－（ＥＯ）_p－（ＰＯ）_q－Ｒ⁶ （３）
式（３）中、Ｒ⁵は水素原子、またはメチル基を示す。Ｒ⁶は水素原子、または炭素数が１以上５以下の炭化水素基を示し、ＥＯはエチレンオキシ基、ＰＯはプロピレンオキシ基を示し、pはエチレンオキシ基の平均付加モル数を示し、１以上１２０以下であり、ｑはプロピレンオキシ基の平均付加モル数を示し、０以上５０以下である。 In one aspect of the present disclosure, semiconducting SWCNTs, at least one of an organic solvent and water, a structural unit A derived from a monomer represented by the following formula (1), and the following formula (3) and a copolymer containing a structural unit B derived from a monomer represented by a semiconducting SWCNT-containing ink.
_CH2 ⁼ CR0-COOM (1)
In formula (1), R ⁰ represents a hydrogen atom or a methyl group. M represents any one of a hydrogen atom, a metal atom, and a group having a structure represented by the following formula (2).

In formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 or more and 2 or less carbon atoms which may have a hydroxyl group.
_CH2 =CR5- ^COO- (EO) _p- (PO) _q -R6 ( ³ )
In formula ( ³ ), R5 represents a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, p represents the average number of added moles of ethyleneoxy groups, and is 1 or more. It is 120 or less, and q represents the average added mole number of propyleneoxy groups, and is 0 or more and 50 or less.

According to the present disclosure, a method for producing a semiconducting SWCNT dispersion, a semiconducting SWCNT, and a metal A method for isolating type SWCNTs can be provided. In one aspect, the present disclosure can provide a method for producing semiconducting SWCNTs and a method for producing an ink containing semiconducting SWCNTs, which includes the above-mentioned production method as one step, and can provide an ink containing semiconducting SWCNTs.

In the present disclosure, by including a specific polymer in the SWCNT dispersion to be separated, both high separation of semiconducting SWCNTs and dispersion stability of semiconducting SWCNTs in the obtained semiconducting SWCNT dispersion are achieved. based on the knowledge that

Although the details of the mechanism by which the effects of the present disclosure are manifested are not clear, it is speculated as follows. In the present disclosure, the SWCNT dispersion to be separated contains the copolymer containing the structural unit A derived from the monomer represented by the above formula (1), so that the semiconducting SWCNTs are selectively On the other hand, since the metallic SWCNT aggregates, by subjecting it to centrifugation, it becomes possible to separate the metallic SWCNT and the semiconducting SWCNT satisfactorily, and the separability of the semiconducting SWCNT is improved. It is assumed that this is possible. In addition, since the copolymer contains the structural unit B derived from the monomer represented by the above formula (3), the dispersion stability of the semiconducting SWCNTs in the resulting semiconducting SWCNT dispersion liquid is good. It is assumed that there are However, the present disclosure should not be construed as being limited to these mechanisms.

式（２）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴はそれぞれ独立に、水素原子、又は水酸基を有していてもよい炭素数が１以上２以下のアルキル基を示す。
ＣＨ₂＝ＣＲ⁵－ＣＯＯ－（ＥＯ）_p－（ＰＯ）_q－Ｒ⁶ （３）
式（３）中、Ｒ⁵は水素原子、またはメチル基を示す。Ｒ⁶は水素原子、または炭素数が１以上５以下の炭化水素基を示し、ＥＯはエチレンオキシ基（以下「ＥＯ基」ともいう）、ＰＯはプロピレンオキシ基（以下「ＰＯ基」ともいう）を示し、pはエチレンオキシ基の平均付加モル数を示し、１以上１２０以下であり、ｑはプロピレンオキシ基の平均付加モル数を示し、０以上５０以下である。 [Method for producing semiconducting SWCNT dispersion, method for separating semiconducting SWCNT and metallic SWCNT]
The present disclosure, in one aspect, relates to a method for producing a semiconducting SWCNT dispersion (hereinafter also referred to as “method for producing a dispersion of the present disclosure”), including the following steps A and B. In another aspect, the present disclosure also relates to a method for separating semiconducting SWCNTs and metallic SWCNTs (hereinafter also referred to as “separation method of the present disclosure”), including the following steps A and B.
(Step A) SWCNTs containing semiconducting SWCNTs and metallic SWCNTs (hereinafter also referred to as “SWCNT mixture”) and a monomer represented by the following formula (1) (hereinafter also referred to as “monomer A”) A copolymer containing a structural unit B derived from a structural unit A derived from and a monomer represented by (3) below (hereinafter also referred to as "monomer B"), and an aqueous medium, SWCNT to be separated A dispersion is prepared.
(Step B) After centrifuging the to-be-separated SWCNT dispersion, a supernatant containing the semiconducting SWCNT is collected from the centrifuged to-be-separated SWCNT dispersion.
_CH2 ⁼ CR0-COOM (1)
In formula (1), R ⁰ represents a hydrogen atom or a methyl group. M represents any one of a hydrogen atom, a metal atom, and a group having a structure represented by the following formula (2).

In formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 or more and 2 or less carbon atoms which may have a hydroxyl group.
_CH2 =CR5- ^COO- (EO) _p- (PO) _q -R6 ( ³ )
In formula ( ³ ), R5 represents a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, EO is an ethyleneoxy group (hereinafter also referred to as "EO group"), PO is a propyleneoxy group (hereinafter also referred to as "PO group") p is the average number of added moles of ethyleneoxy groups and is 1 or more and 120 or less, and q is the average number of added moles of propyleneoxy groups and is 0 or more and 50 or less.

In the present disclosure, "collecting the supernatant containing the semiconducting SWCNT" means that the semiconductor in the SWCNT dispersion to be separated obtained in the step A in the method for producing a dispersion of the present disclosure and the separation method of the present disclosure. It means collecting a supernatant liquid in which the ratio of the semiconducting SWCNTs is improved with respect to the ratio of the SWCNTs of the metallic type and the SWCNTs of the metallic type, and the supernatant liquid is the dispersion of the SWCNTs of the semiconducting type. The present disclosure does not exclude that the supernatant contains relatively low amounts of metallic SWCNTs compared to semiconducting SWCNTs. When the separability of semiconducting SWCNTs is improved, the ratio of semiconducting SWCNTs in the SWCNTs in the supernatant increases, making the material more useful as a material for semiconductor devices.

In the step B of the method for producing a dispersion of the present disclosure and the separation method of the present disclosure, collecting the supernatant can be performed, for example, by separating the supernatant from its remainder. The residue includes sediment containing relatively more metallic SWCNTs than semiconducting SWCNTs.

[Step A]
In one or more embodiments, the step A in the method for producing a dispersion of the present disclosure and the separation method of the present disclosure includes, in one or more embodiments, at least a structural unit A derived from the monomer A and a After preparing a mixed solution containing a copolymer containing the structural unit B, the SWCNT mixture, and an aqueous medium (hereinafter sometimes abbreviated as “mixed solution A”), the mixed solution A is subjected to dispersion treatment. subject to Mixture A can be prepared, for example, by adding the SWCNT mixture to an aqueous solution of the copolymer.

[Copolymer containing structural unit A derived from monomer A and structural unit B derived from monomer B]
The copolymer is water-soluble from the viewpoint of improving the separability of semiconducting SWCNTs. In the present disclosure, "water-soluble" means that 1 g or more of a polymer dissolves in 100 g of water at 20°C.

(Structural unit A derived from monomer A)
The structural unit A contained in the copolymer is a structural unit derived from the monomer A represented by the above formula (1). In the above formula (1), R ⁰ is preferably a methyl group from the viewpoint of improving the separability of semiconducting SWCNTs. In the above formula (1), M is a hydrogen atom, a metal atom, or a group of the structure represented by the above formula (2) from the viewpoint of improving the separability and productivity of semiconducting SWCNTs, but a semiconductor From the viewpoint of improving the separability of type SWCNT, improving productivity, and improving versatility, it is preferably a hydrogen atom or a group having a structure represented by the above formula (2), more preferably a hydrogen atom. . Monomer A that provides structural unit A is preferably methacrylic acid.

(Structural unit B derived from monomer B)
The structural unit B contained in the copolymer is a structural unit derived from the monomer B represented by the above formula (3). The structural unit B contained in the copolymer may be of one type, or may be a combination of two or more types.

In the above formula (3), R ⁵ is preferably a methyl group from the viewpoint of improving the separability of semiconducting SWCNTs.

In the above formula (3), R ⁶ is a hydrogen atom or a carbon number of 1 from the viewpoint of improving the separation of semiconducting SWCNTs and the dispersion stability of a semiconducting SWCNT dispersion liquid, and from the viewpoint of availability of monomers. Above and below 5 hydrocarbon groups are shown. When R ⁶ is a hydrocarbon group, the number of carbon atoms is preferably 1 from the viewpoint of improving the separation of semiconducting SWCNTs and the dispersion stability of a dispersion of semiconducting SWCNTs, and from the viewpoint of availability of monomers. 4 or less, more preferably 1 or more and 3 or less. Examples of hydrocarbon groups for R ⁶ include alkyl groups. Specific examples of R ⁶ include at least one selected from a butyl group, an ethyl group, a methyl group, and a hydrogen atom. is preferred, and a methyl group is more preferred. In the copolymer, R ⁶ is a hydrocarbon group, and the number of carbon atoms is preferably 1 or more and 4 or less, from the viewpoint of improving the separation property of the semiconducting SWCNT and the dispersion stability of the semiconducting SWCNT dispersion. , more preferably 1 or more and 3 or less structural units B, and a structural unit B in which R ⁶ is hydrogen. The terminal carbon number of the structural unit B, that is, the carbon number of R ⁶ can be calculated from the chemical shift in nuclear magnetic resonance, specifically by the method described in Examples.
Monomer B that provides structural unit B is preferably 2-hydroxyethyl methacrylate (HEMA), butoxypolyethylene glycol methacrylate, ethoxypolyethylene glycol methacrylate, methoxypolyethylene glycol (meth)acrylate (PEG(M)A), More preferably, it contains methoxy polyethylene glycol methacrylate (PEGMA).

In formula (3), p is 1 or more from the viewpoint of improving the separability of semiconducting SWCNTs, and is 120 or less from the viewpoint of improving separability of semiconducting SWCNTs and the availability of monomers. , preferably 100 or less, more preferably 90 or less, even more preferably 60 or less, even more preferably 45 or less, and even more preferably 25 or less.

In formula (3), q is 0 or more and 50 or less, preferably 0 or more and 30 or less, from the viewpoint of the water solubility of the copolymer, the separation tendency of the semiconducting SWCNT, and the availability of the monomer. , more preferably 0 or more and 10 or less, still more preferably 0 or more and 5 or less, still more preferably 0 or more and 3 or less, still more preferably 0.

In the formula (3), q/(p+q) is preferably 0.7 or less, more preferably 0.7 or less, from the viewpoint of the water solubility of the copolymer, the improvement of the separability of the semiconducting SWCNT, and the availability of the monomer. is 0.4 or less, more preferably 0.

In formula (3), the addition order of the EO group and the PO group does not matter, and when q is 2 or more, block bonding or random bonding may be used.

When the structural unit B contained in the copolymer is a combination of two or more, from the viewpoint of improving the separability of the semiconducting SWCNT, the structural unit B ₁ having an average added mole number p of EO groups of 4 or more and 120 or less and a structural unit B ₂ in which p is 1 or more and less than 4. The average added mole number p of the structural unit B ₁ is preferably 100 or less, more preferably 90 or less, still more preferably 60 or less, still more preferably 45 or less, and even more preferably, from the viewpoint of improving the separability of the semiconducting SWCNT. is 25 or less. The average added mole number p of the structural unit B ₂ is preferably 3 or less, more preferably 2 or less, and still more preferably 1 from the viewpoint of improving the separability of the semiconducting SWCNT.

R ⁶ of the structural unit B ₁ is preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms. is a hydrocarbon group of R ⁶ of structural unit B ₂ is preferably a hydrogen atom.

When the structural unit B contained in the copolymer is a combination of the structural unit B ₁ and the structural unit B ₂ , the molar ratio of the structural unit B ₁ and the structural unit B ₂ in the copolymer (B ₁ /B ₂ ) is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.05 or more from the viewpoint of improving the separability of semiconducting SWCNTs. From the viewpoint, it is preferably 0.5 or less, more preferably 0.4 or less, and still more preferably 0.3 or less.

When the structural unit B contained in the copolymer is a combination of the structural unit B ₁ and the structural unit B ₂ , the mass ratio of the structural unit B ₁ and the structural unit B ₂ in the copolymer (B ₁ /B ₂ ) is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.4 or more from the viewpoint of improving the separability of semiconducting SWCNTs. From the viewpoint, it is preferably 5 or less, more preferably 3 or less, and still more preferably 1 or less.

The content (% by mass) of the structural unit A in all the structural units of the copolymer is preferably more than 0% by mass, more preferably 1% by mass or more, and still more preferably from the viewpoint of improving the separability of semiconducting SWCNTs. is 2% by mass or more, still more preferably 3% by mass or more, and from the viewpoint of improving the dispersion stability of the semiconducting SWCNT dispersion, preferably 80% by mass or less, more preferably 50% by mass or less, and further It is preferably 30% by mass or less, and still more preferably 20% by mass or less.

The content (mol%) of the structural unit A in all the structural units of the copolymer is preferably more than 0 mol%, more preferably 1 mol% or more, and still more preferably 3 mol, from the viewpoint of improving the separability of the semiconducting SWCNT. % or more, still more preferably 5 mol% or more, still more preferably 8 mol% or more, and from the viewpoint of improving the dispersion stability of the semiconducting SWCNT dispersion, preferably less than 100 mol%, more preferably 90 mol% or less, and further It is preferably 80 mol % or less, still more preferably 60 mol % or less, still more preferably 40 mol % or less, and even more preferably 25 mol % or less.

The content (% by mass) of the structural unit B in all the structural units of the copolymer is preferably more than 10% by mass, more preferably 50% by mass, from the viewpoint of improving the dispersion stability of the semiconducting SWCNT dispersion. Above, more preferably 70% by mass or more, still more preferably 80% by mass or more, preferably less than 100% by mass, more preferably 97% by mass or less, still more preferably from the viewpoint of improving the separability of semiconducting SWCNTs It is 95% by mass or less.

The content (mol%) of the structural unit B in all the structural units of the copolymer is preferably more than 0 mol%, more preferably 10 mol% or more, from the viewpoint of improving the dispersion stability of the semiconducting SWCNT dispersion. More preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 50 mol% or more, from the viewpoint of improving the separation of semiconducting SWCNTs, preferably less than 100 mol%, more preferably 97 mol% or less, and further It is preferably 95 mol % or less, and still more preferably 92 mol % or less.

The total content (% by mass) of the structural unit A and the structural unit B in all the structural units of the copolymer is, from the viewpoint of improving the separability of the semiconducting SWCNT and the dispersion stability of the semiconducting SWCNT dispersion liquid, It is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and 100% by mass or less. From the viewpoint of improving the separability of semiconducting SWCNTs, it is more preferably substantially 100% by mass.

The total content (mol%) of the structural unit A and the structural unit B in all the structural units of the copolymer is, from the viewpoint of improving the separability of the semiconducting SWCNT and the dispersion stability of the semiconducting SWCNT dispersion liquid, It is preferably 80 mol % or more, more preferably 90 mol % or more, still more preferably 95 mol % or more, still more preferably 99 mol % or more, and 100 mol % or less. From the viewpoint of improving the separability of semiconducting SWCNTs, it is more preferably substantially 100 mol %.

The copolymer may contain a structural unit C other than the structural units A and B as long as the effects of the present disclosure are not impaired. Structural unit C may be of one type or a combination of two or more types. Examples of the monomer C that provides the structural unit C include carboxylic acid-based monomers other than the monomer A such as maleic acid, and structural units derived from nonionic monomers other than the structural unit B. At least one selected from (meth)acrylic ester-based monomers, (meth)acrylamide-based monomers, styrene-based monomers, and (meth)acrylonitrile-based monomers as the nonionic monomer Among these, (meth)acrylic acid ester-based monomers are preferred.

When the monomer C is a (meth)acrylic acid ester-based monomer, examples of the monomer C include methyl (meth)acrylate, ethyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. , lauryl (meth)acrylate, stearyl (meth)acrylate, and benzyl (meth)acrylate.

When the monomer C is a (meth)acrylamide-based monomer, examples of the monomer C include at least one selected from acrylamide, methacrylamide, dimethylacrylamide, and dimethylmethacrylamide.

When the monomer C is a styrenic monomer, examples of the monomer C include styrene and methylstyrene.

When the monomer C is a (meth)acrylonitrile-based monomer, examples of the monomer C include acrylonitrile and methacrylonitrile.

The content of the structural unit C in the copolymer is preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of achieving both improved separability of semiconducting SWCNTs and dispersion stability of the semiconducting SWCNT dispersion. , more preferably 5% by mass or less, still more preferably 1% by mass or less, and even more preferably substantially free. Here, "substantially free" means that it is not intentionally contained, for example, it is contained in the raw material monomers constituting the structural unit A and the structural unit B, and is unintentionally included. case falls under “substantially not included”.

The mass ratio (A/B) of the structural unit A and the structural unit B in the copolymer is preferably greater than 0, more preferably 0.01 or more, and still more preferably from the viewpoint of improving the separability of semiconducting SWCNTs. is 0.03 or more, still more preferably 0.05 or more, and from the viewpoint of improving the dispersion stability of the semiconducting SWCNT dispersion, preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less , still more preferably 1.5 or less, still more preferably 0.5 or less, still more preferably 0.4 or less.

The molar ratio (A/B) of the structural unit A and the structural unit B in the copolymer is preferably greater than 0, more preferably 0.01 or more, and still more preferably from the viewpoint of improving the separability of the semiconducting SWCNT. is 0.05 or more, still more preferably 0.1 or more, and from the viewpoint of improving the dispersion stability of the semiconducting SWCNT dispersion, preferably 30 or less, more preferably 10 or less, and even more preferably 5 or less , still more preferably 3 or less, still more preferably 2 or less, still more preferably 1.1 or less, and even more preferably 0.5 or less.

The weight-average molecular weight of the copolymer is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, still more preferably 4, from the viewpoint of improving the separability of semiconducting SWCNTs. 000 or more, preferably 250,000 or less, more preferably 150,000 or less, even more preferably 120,000 or less, still more preferably 110,000 or less from the viewpoint of improving the separability of semiconducting SWCNTs. In the present disclosure, the weight average molecular weight of the copolymer is determined by gel permeation chromatography, and specifically, can be measured by the method described in Examples.

The mass ratio (copolymer/SWCNT) of the copolymer to the SWCNTs in the mixed liquid A and in the SWCNT dispersion to be separated is, from the viewpoint of improving the separability of semiconducting SWCNTs and improving productivity, It is preferably 0.5 or more, more preferably 1 or more, still more preferably 2 or more, still more preferably 4 or more, and from the viewpoint of improving the separation of semiconducting SWCNTs and improving productivity, it is preferably 100 Below, it is more preferably 70 or less, still more preferably 50 or less, and even more preferably 20 or less.

The content of the copolymer in the mixed liquid A and in the SWCNT dispersion to be separated is preferably 0.05% by mass or more, from the viewpoint of improving the separability of semiconducting SWCNTs and improving productivity, More preferably 0.1% by mass or more, still more preferably 0.15% by mass or more, still more preferably 0.2% by mass or more, and from the same viewpoint, preferably 10% by mass or less, more preferably It is 7% by mass or less, more preferably 5% by mass or less.

[SWCNT]
There are no particular restrictions on the mixed solution A and the SWCNTs used in preparing the SWCNT dispersion to be separated. SWCNTs are synthesized by conventionally known synthesis methods such as the HiPco method and the e-DIPS method, and may include those with various winding methods and diameters. Although metallic SWCNTs and semiconducting SWCNTs may be included in any ratio, generally synthesized SWCNTs are SWCNT mixtures containing about 1/3 metallic SWCNTs and about 2/3 semiconducting SWCNTs. be.

The average diameter of SWCNTs is preferably 0.5 nm or more, more preferably 0.8 nm or more, from the viewpoint of improving the separability of semiconducting SWCNTs, and from the same viewpoint, preferably 3 nm or less, more preferably 2 nm. It is below. The average diameter of SWCNTs can be calculated by measuring and averaging the diameters of 10 or more CNTs from an image obtained using a transmission electron microscope.

The average length of the SWCNTs is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more from the viewpoint of electrical properties. From the viewpoint of improving productivity, it is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 20 μm or less, and even more preferably 10 μm or less. The average length of SWCNTs can be calculated, for example, by measuring the lengths of 10 or more CNTs from an image obtained using a transmission electron microscope and averaging the lengths.

The content of SWCNTs in the mixed liquid A and in the SWCNT dispersion to be separated is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, from the viewpoint of improving the separability of semiconducting SWCNTs. , More preferably 0.03% by mass or more, and from the viewpoint of improving the separability of semiconducting SWCNTs and improving productivity, preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably It is 0.5% by mass or less.

[Aqueous medium]
The mixed solution A and the SWCNT dispersion to be separated contain an aqueous medium as a dispersion medium. The aqueous medium is preferably water, and water is preferably pure water, ion-exchanged water, purified water, or distilled water, more preferably pure water, from the viewpoint of improving the separability of semiconducting SWCNTs and improving productivity.

The mixed liquid A and the SWCNT dispersion to be separated may contain lower alcohols such as methanol, ethanol, and isopropyl alcohol, and water-soluble organic solvents such as acetone, tetrahydrofuran, and dimethylformamide, in addition to water, as aqueous media. good.

When the aqueous medium is a combination of water and a dispersion medium other than water, the proportion of water in the dispersion medium is preferably 70% by mass or more, more preferably 80% by mass, from the viewpoint of improving the separability of semiconducting SWCNTs. % or more, more preferably 90 mass % or more.

The content of the aqueous medium in the mixed liquid A and in the SWCNT dispersion to be separated is preferably 85% by mass or more, more preferably 92% by mass, from the viewpoint of improving the separability of semiconducting SWCNTs and improving productivity. % by mass or more, more preferably 96% by mass or more, and from the same viewpoint, preferably 99.9% by mass or less, more preferably 99.8% by mass or less, still more preferably 99.5% by mass or less, Even more preferably, it is 99.0% by mass or less.

The dispersion treatment of the mixed liquid A can be performed using, for example, a dispersing machine such as a bath-type ultrasonic dispersing machine, a homomixer, a high-pressure homogenizer, an ultrasonic homogenizer, a jet mill, a bead mill, or a miller.

In step A, defoaming treatment may be performed on mixed liquid A before dispersion treatment.

[Step B]
In the step B in the method for producing a dispersion of the present disclosure and the separation method of the present disclosure, the SWCNT dispersion to be separated obtained in the step A is subjected to centrifugation, and the semiconductor in the centrifuged SWCNT dispersion to be separated The supernatant containing type SWCNTs is collected. The supernatant has a higher ratio of semiconducting SWCNTs than the ratio of semiconducting SWCNTs and metallic SWCNTs in the SWCNT dispersion to be separated before centrifugation. The ratio varies depending on the centrifugation conditions, etc., but the rotation speed of the centrifuge is preferably 5,000 rpm or more, more preferably 10,000 rpm or more, from the viewpoint of improving the separability of semiconducting SWCNTs and improving productivity. From the same point of view, it is preferably 100,000 rpm or less, more preferably 70,000 rpm or less. Gravitational acceleration of the centrifuge is preferably 10 kG or more, more preferably 50 kG or more, from the viewpoint of improving the separability of semiconducting SWCNTs and improving productivity, and from the same viewpoint, preferably 1000 kG or less, more preferably. is 500 kG or less.

[Method for producing semiconducting SWCNT and semiconducting SWCNT]
Semiconducting SWCNTs can be produced by extracting the semiconducting SWCNTs from the semiconducting SWCNT dispersion produced by the method for producing a semiconducting SWCNT dispersion of the present disclosure. The semiconducting SWCNTs can be collected from the semiconducting SWCNT dispersion liquid, for example, by filtering the semiconducting SWCNTs from the semiconducting SWCNT dispersion liquid with a membrane filter and then drying it. When filtering the semiconducting SWCNTs from the semiconducting SWCNT dispersion, the semiconducting SWCNTs in the semiconducting SWCNT dispersion may be filtered after pretreatment such as reprecipitation. Alternatively, it can be carried out by drying the semiconducting SWCNT dispersion and removing the co-existing copolymer by means of washing, thermal decomposition, or the like. Therefore, in one aspect, the present disclosure includes a step of filtering the semiconducting SWCNT dispersion obtained by the method for producing a semiconducting SWCNT dispersion of the present disclosure to collect the semiconducting SWCNTs. The present invention relates to a method (hereinafter also referred to as “method A for producing semiconducting SWCNTs of the present disclosure”). In another aspect, the present disclosure provides a step of drying the semiconducting SWCNT dispersion obtained by the method for producing a semiconducting SWCNT dispersion of the present disclosure to obtain a mixture containing the semiconducting SWCNTs and the copolymer. and a step of removing the copolymer from the mixture to collect semiconducting SWCNTs (hereinafter also referred to as “method B for producing semiconducting SWCNTs of the present disclosure”). In another aspect, the present disclosure also relates to semiconducting SWCNTs obtained by the method A or B for producing semiconducting SWCNTs of the present disclosure (hereinafter also referred to as “semiconducting SWCNTs of the present disclosure”).

[Method for producing semiconducting SWCNT-containing ink]
In one aspect of the present disclosure, a method for producing a semiconducting SWCNT-containing ink (hereinafter referred to as " Also referred to as "method for producing semiconducting SWCNT-containing ink of the present disclosure"). An embodiment of the method for producing a semiconducting SWCNT-containing ink according to the present disclosure includes, for example, the method A or B for producing a semiconducting SWCNT according to the present disclosure as one step, and a step of mixing at least one of them and optionally at least one of a surfactant and a resin. Further, another embodiment of the method for producing a semiconducting SWCNT-containing ink of the present disclosure includes, for example, the method for producing a semiconducting SWCNT dispersion of the present disclosure as one step, and the semiconducting SWCNT dispersion and, if necessary, and mixing at least one of an organic solvent, a surfactant and a resin that are miscible with the dispersion.

Examples of the organic solvent include aliphatic solvents such as n-hexane, n-octane and n-decane; alicyclic solvents such as cyclohexane; aromatic solvents such as benzene and toluene; Examples include alcohol solvents, glycol ether solvents such as diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and butyl cellosolve. The semiconducting SWCNT-containing ink may further contain, from the viewpoint of film-forming property improvement, a resin that can be dissolved or dispersed in a solvent, for example, a polystyrene resin, an acrylic resin, a vinyl resin, etc., or as a dispersant. It may contain known surfactants and other additives. The content of semiconducting SWCNTs in the ink containing semiconducting SWCNTs may be appropriately set according to the application.

[Ink containing semiconducting SWCNT]
In one aspect, the present disclosure includes semiconducting single-layer SWCNTs, at least one of an organic solvent and water, a structural unit A derived from the monomer represented by the above formula (1), and the above formula (3) A semiconducting SWCNT-containing ink (hereinafter also referred to as "semiconducting SWCNT-containing ink of the present disclosure") containing a copolymer containing a structural unit B derived from a monomer represented by
One embodiment of the semiconducting SWCNT-containing ink of the present disclosure is represented by at least the semiconducting SWCNT of the present disclosure, the structural unit A derived from the monomer represented by the above formula (1), and the above formula (3). and at least one of an organic solvent and water, and optionally a surfactant and a resin.

[Method for manufacturing a semiconductor device]
In one aspect, the present disclosure includes a step of forming a semiconductor layer by printing or applying a semiconducting SWCNT-containing ink obtained by the method for producing a semiconducting SWCNT-containing ink of the present disclosure on a substrate. It relates to a manufacturing method.

Further, in another aspect, the present disclosure is a method for manufacturing a semiconductor device comprising a substrate and a gate electrode, a source electrode and a drain electrode arranged on the substrate, wherein the ink containing the semiconducting SWCNT is printed. Alternatively, the present invention relates to a method of manufacturing a semiconductor device including a step of forming a semiconductor circuit or a semiconductor film (semiconductor layer) by coating. Examples of the method for printing the semiconducting SWCNT-containing ink include inkjet printing, screen printing, offset printing, letterpress printing, and the like. A step of forming a circuit by etching or the like after forming a semiconductor film by printing or coating may be included.

EXAMPLES The present disclosure will be described in more detail below with reference to examples, but these are examples and the present disclosure is not limited to these examples.

1. Measurement method of various parameters [Measurement of weight average molecular weight of copolymer]
The weight average molecular weight of the copolymer used to prepare the SWCNT dispersion to be separated was measured under the following conditions using a gel permeation chromatography (hereinafter also referred to as "GPC") method.
<GPC conditions>
Measuring device: HLC-8320GPC (manufactured by Tosoh Corporation)
Column: α-M + α-M (manufactured by Tosoh Corporation)
Eluent: N,N-dimethylformamide (DMF) solution of 60mmol/L _H3PO4 and _50mmol /L LiBr Flow rate: 1.0mL/min
Column temperature: 40°C
Detection: RI
Sample size: 0.5 mg/mL
Standard material: Monodisperse polystyrene (manufactured by Tosoh Corporation)

[Method for measuring the number of moles of EO and PO added]
The number of moles of EOPO added to the copolymer used for preparing the separated SWNT dispersion was measured under the following conditions using nuclear magnetic resonance spectroscopy (hereinafter also referred to as “NMR”). The number of moles of EO and PO added was calculated from the integrated value of the chemical shift.
<NMR conditions>
Measuring device: Vnmrs400 (manufactured by Agilent)
Measurement solvent: heavy chloroform (containing 0.05% TMS) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
Measurement chemical species: 1H

[Measurement method of terminal carbon number of PEGMA in copolymer]
The number of terminal carbon atoms of PEGMA in the copolymer used for preparing the separated SWNT dispersion was measured under the following conditions using nuclear magnetic resonance spectroscopy (hereinafter also referred to as "NMR"). The terminal carbon number was calculated from the integrated value of the chemical shift.
<NMR conditions>
Measuring device: Vnmrs400 (manufactured by Agilent)
Measurement solvent: heavy chloroform (containing 0.05% TMS) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
Measurement chemical species: 1H, 13C

[Evaluation of water solubility]
1 g of the copolymer was added to 100 g of water at 20° C., stirred for 5 minutes, and the presence or absence of insoluble matter was visually observed. If no insoluble matter was observed, it was judged to be water soluble. In Tables 1 and 2, A is indicated when it is judged to be water soluble, and B is indicated when it is judged not to be water soluble.

[Measurement of average diameter and average length of SWCNT]
The average diameter and length of SWCNTs were calculated by measuring the diameters and lengths of 10 or more CNTs from an image obtained using a transmission electron microscope and averaging them.

2. Production of copolymers a to i [copolymer a]
A reaction vessel equipped with a stirrer, reflux tube, thermometer, dropping funnel 1 and dropping funnel 2 was charged with 15 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the reaction system was replaced with nitrogen while stirring. °C. Monomer (methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 15 g (71.2 mol%) and methoxypolyethylene glycol (9) monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "M-90G" 35 g in dropping funnel 1 (28.8 mol%)) and 10 g of ethanol was added to the dropping funnel 2, and 1.59 g of 3-mercapto-1,2-propanediol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (6. 0 mol % of the total monomers) and 0.304 g (0.304 g of 2,2′-azobis(2,4-dimethylvaleronitrile) (“V-65B” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a polymerization initiator. 5 mol % of the total monomer) and 50.5 g of ethanol were prepared and added dropwise to the reactor over 1 hour at the same time.After the drop was completed, the mixture was aged while stirring over 1 hour to complete the reaction. , to obtain copolymer a.

[Copolymers b to i]
Copolymers b to i were obtained in the same manner as in the production method of copolymer a, except that the monomers, amount of monomers, amount of chain transfer agent, and amount of polymerization initiator shown in Table 1 were changed.
The physical properties of the obtained copolymers a to i are shown in Table 1 below.

The monomers used in the production of polymers a to i are as follows.
(monomer A)
MAA: methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (Fuji Film Wako Pure Chemical Co., Ltd. "special grade")
(monomer B ₁ )
PEG (9) MA: methoxypolyethylene glycol (9) monomethacrylate ["M-90G" manufactured by Shin-Nakamura Chemical Co., Ltd.] (in formula (3), R ⁶ = methyl, R ⁵ = methyl, p = 9, q=0)
(monomer B ₁ )
PEG (23) MA: methoxypolyethylene glycol (23) monomethacrylate [“M-230G” manufactured by Shin-Nakamura Chemical Co., Ltd.] (in formula ^{( 3} ), R = methyl, R = methyl, p = 23, q=0)
(monomer B ₁ )
PEG (90) MA: methoxypolyethylene glycol (90) monomethacrylate [“M-900G” manufactured by Shin-Nakamura Chemical Co., Ltd.] (in formula ^{( 3} ), R = methyl, R = methyl, p = 90, q=0)
(monomer B ₁ )
PEG (20) PG (3) MA: methoxypolyethylene glycol (20) polypropylene glycol (3) monomethacrylate ["M-0320PE" manufactured by Shin-Nakamura Chemical Co., Ltd.] (in formula ( ³ ), R = methyl, R5 = methyl, p = 20, q = ³ )
(monomer B ₁ )
PEG (45) MA: methoxypolyethylene glycol (45) monomethacrylate [“M-450G” manufactured by Shin-Nakamura Chemical Co., Ltd.] (in formula ^{( 3} ), R = methyl, R = methyl, p = 45, q=0)
(monomer B ₂ )
HEMA: 2-hydroxyethyl methacrylate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (in formula ( ³ ), R = H, R = methyl, p = ¹ , q = 0)
(others)
PDEA: Phenoxydioxyethylene acrylate ["Light acrylate P2H-A" manufactured by Kyoeisha Chemical Co., Ltd.]

3. Preparation of semiconducting SWCNT dispersion [Examples 1 to 8]
A SWCNT mixture synthesized by the HiPco method (“HiPco-Raw” manufactured by NanoIntegris) was added to 30 mL of a 0.5% by mass aqueous solution in which each of the copolymers shown in Table 1 was dissolved in ultrapure water (manufactured by Wako Pure Chemical Industries). , average diameter: 0.8-1.2 nm, average length: 0.4-0.7 μm) was added to obtain a mixed solution.
Then, while stirring the mixed solution with a stirrer, it was dispersed with an ultrasonic homogenizer ("450D" manufactured by BRANSON) for 10 minutes under the conditions of AMPLITUDE 30% and 10 ° C. to obtain a separated SWCNT dispersion of Examples 1 to 8. rice field. Table 2 shows the type and content of each component in each to-be-separated SWCNT dispersion. The contents of the SWCNT mixture and copolymer in the SWCNT dispersion to be separated are as shown in Table 2, and the content of the aqueous medium is the remainder after removing the SWCNT mixture and copolymer.
An ultracentrifuge ("CS100GXII" manufactured by Hitachi Koki Co., Ltd., rotor S50A) was used for the obtained SWCNT dispersion to be separated, under the conditions of a rotation speed of 50000 rpm, a gravitational acceleration of 210 kG, and 20 ° C. for 30 minutes. Centrifugation was performed. After that, 80% of the supernatant liquid was collected from the liquid surface on a volume basis so as not to stir up the precipitated sediments, and semiconducting SWCNT dispersion liquids of Examples 1 to 8 were obtained.

[Comparative Example 1]
A separated SWCNT dispersion and a supernatant (semiconducting SWCNT dispersion) of Comparative Example 1 were obtained in the same manner as in Example 1, except that the copolymer f was used instead of the copolymer a. The contents of the SWCNT mixture and copolymer in the SWCNT dispersion to be separated are as shown in Table 2, and the content of the aqueous medium is the remainder after removing the SWCNT mixture and the compound.

なお、使用したＳＷＣＮＴ（ＨＩＰＣＯ）は、７３０ｎｍ付近に半導体型ＳＷＣＮＴに固有の吸収波長を有し、４８０ｎｍ付近に金属型ＳＷＣＮＴに固有の吸収波長を有する。 4. Evaluation [separability evaluation]
Absorbance is measured using an ultraviolet-visible-near-infrared spectrophotometer (“UV-3600Plus” manufactured by Shimadzu Corporation) capable of measuring from visible light to infrared light. Then, the ratio of the peak intensity of the absorption wavelength peculiar to the semiconducting SWCNT and the peak intensity of the absorption wavelength peculiar to the metallic SWCNT was used as an evaluation value of the separability of the semiconducting SWCNT. The higher the calculated value, the higher the separability of the semiconducting SCNT can be evaluated. If the value is 1.2 or more, the separability of the semiconducting SCNT is sufficiently high. Table 2 shows the results.

The SWCNTs (HIPCO) used have an absorption wavelength around 730 nm unique to semiconducting SWCNTs, and an absorption wavelength around 480 nm unique to metallic SWCNTs.

[Dispersion stability evaluation]
The dispersed state of the semiconducting SWCNTs in the semiconducting SWCNT dispersion after being left at room temperature of 25° C. for 2 weeks was evaluated according to the following evaluation criteria, and the results are shown in Table 2.
(Evaluation criteria)
A: Aggregates cannot be visually confirmed.
B: Several (less than 6) aggregates can be visually confirmed.
C: Many aggregates can be visually confirmed.

As shown in Table 2, in Examples 1 to 8, compared to Comparative Example 1, both high separability of semiconducting SWCNTs and dispersion stability of semiconducting SWCNTs in the semiconducting SWCNT dispersion liquid were satisfactorily achieved. there is

As described above, according to the method for producing a semiconducting SWCNT dispersion of the present disclosure, both high separability of semiconducting SWCNTs and dispersion stability of semiconducting SWCNTs in the semiconducting SWCNT dispersion can be satisfactorily achieved. , an improvement in the quality of semiconducting SWCNT-containing inks can be expected.

Claims (10)

a step of preparing a dispersion of single-walled carbon nanotubes to be separated, which contains single-walled carbon nanotubes including semiconducting single-walled carbon nanotubes and metallic single-walled carbon nanotubes, an aqueous medium, and a polymer;
After centrifuging the single-walled carbon nanotube dispersion to be separated, collecting a supernatant liquid containing the semiconducting single-walled carbon nanotubes from the centrifuged single-walled carbon nanotube dispersion,
The polymer is a copolymer containing a structural unit A derived from a monomer represented by the following formula (1) and a structural unit B derived from a monomer represented by the following formula (3) A method for producing a semiconducting single-walled carbon nanotube dispersion.
_CH2 ⁼ CR0-COOM (1)
In formula (1), R ⁰ represents a hydrogen atom or a methyl group. M represents any one of a hydrogen atom, a metal atom, and a group having a structure represented by the following formula (2).

In formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 or more and 2 or less carbon atoms which may have a hydroxyl group.
_CH2 =CR5- ^COO- (EO) _p- (PO) _q -R6 ( ³ )
In formula ( ³ ), R5 represents a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, p represents the average number of added moles of ethyleneoxy groups, and is 1 or more. It is 120 or less, and q represents the average added mole number of propyleneoxy groups, and is 0 or more and 50 or less. 2. The method for producing a semiconducting single-walled carbon nanotube dispersion according to claim 1, wherein the content of said structural unit A in all structural units of said copolymer is more than 0 mol % and not more than 90 mol %. 3. The method for producing a semiconducting single-walled carbon nanotube dispersion according to claim 1, wherein the content of said structural unit B in all structural units of said copolymer is 10 mol % or more and less than 100 mol %. 3. The method for producing a semiconducting single-walled carbon nanotube dispersion according to claim 1 , wherein the terminal structure R6 of the monomer represented by formula ( ³ ) is a hydrogen atom or a methyl group. 3. The dispersion of semiconducting single-walled carbon nanotubes according to claim 1 , wherein the single-walled carbon nanotubes used for preparing the dispersion of single-walled carbon nanotubes to be separated have an average diameter of 0.5 nm or more and 3 nm or less. Production method. A semiconductor comprising a step of filtering the semiconducting single-walled carbon nanotube dispersion obtained by the method for producing a semiconducting single-walled carbon nanotube dispersion according to claim 1 or 2 to collect the semiconducting single-walled carbon nanotubes. A method for producing single-walled carbon nanotubes. A mixture containing the semiconducting single-walled carbon nanotubes and the copolymer obtained by drying the semiconducting single-walled carbon nanotube dispersion obtained by the method for producing a semiconducting single-walled carbon nanotube dispersion according to claim 1 or 2 and removing the copolymer from the mixture to collect semiconducting single-walled carbon nanotubes. a step of preparing a dispersion of single-walled carbon nanotubes to be separated, which contains single-walled carbon nanotubes including semiconducting single-walled carbon nanotubes and metallic single-walled carbon nanotubes, an aqueous medium, and a polymer;
After centrifuging the single-walled carbon nanotube dispersion to be separated, collecting a supernatant liquid containing the semiconducting single-walled carbon nanotubes from the centrifuged single-walled carbon nanotube dispersion,
The polymer is a copolymer containing a structural unit A derived from a monomer represented by the following formula (1) and a structural unit B derived from a monomer represented by the following formula (3) A method for separating semiconducting single-walled carbon nanotubes and metallic single-walled carbon nanotubes.
_CH2 ⁼ CR0-COOM (1)
In formula (1), R ⁰ represents a hydrogen atom or a methyl group. M represents any one of a hydrogen atom, a metal atom, and a group having a structure represented by the following formula (2).

In formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 or more and 2 or less carbon atoms which may have a hydroxyl group.
_CH2 =CR5- ^COO- (EO) _p- (PO) _q -R6 ( ³ )
In formula ( ³ ), R5 represents a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, p represents the average number of added moles of ethyleneoxy groups, and is 1 or more. It is 120 or less, and q represents the average added mole number of propyleneoxy groups, and is 0 or more and 50 or less. A method for producing an ink containing a semiconducting single-walled carbon nanotube, comprising the production method according to claim 1 or 2 as one step. A semiconducting single-walled carbon nanotube, at least one of an organic solvent and water, a structural unit A derived from a monomer represented by the following formula (1), and a unit represented by the following formula (3) A semiconducting single-walled carbon nanotube-containing ink comprising a copolymer containing a structural unit B derived from a polymer.
_CH2 ⁼ CR0-COOM (1)
In formula (1), R ⁰ represents a hydrogen atom or a methyl group. M represents any one of a hydrogen atom, a metal atom, and a group having a structure represented by the following formula (2).

In formula (2), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 or more and 2 or less carbon atoms which may have a hydroxyl group.
_CH2 =CR5- ^COO- (EO) _p- (PO) _q -R6 ( ³ )
In formula ( ³ ), R5 represents a hydrogen atom or a methyl group. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, EO represents an ethyleneoxy group, PO represents a propyleneoxy group, p represents the average number of added moles of ethyleneoxy groups, and is 1 or more. It is 120 or less, and q represents the average added mole number of propyleneoxy groups, and is 0 or more and 50 or less.